JP2000026630A - Production of mica tape - Google Patents
Production of mica tapeInfo
- Publication number
- JP2000026630A JP2000026630A JP14283699A JP14283699A JP2000026630A JP 2000026630 A JP2000026630 A JP 2000026630A JP 14283699 A JP14283699 A JP 14283699A JP 14283699 A JP14283699 A JP 14283699A JP 2000026630 A JP2000026630 A JP 2000026630A
- Authority
- JP
- Japan
- Prior art keywords
- curing agent
- epoxy resin
- resin
- room temperature
- backing material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】この発明は、集成マイカ箔
に、電気絶縁用プリプレグを裏打ち材側に貼り合わせて
成るマイカテープの製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a mica tape comprising a laminated mica foil and a prepreg for electrical insulation bonded to a backing material.
【０００２】[0002]
【従来の技術】従来、電気機器用絶縁として用いられる
プリプレグ類は、例えば、特開平２−３４６３９号公報
に示されるように、エポキシ樹脂、ポリエステル樹脂、
シリコン樹脂、ポリイミド樹脂等、通常知られている熱
硬化性樹脂を溶剤に溶かした溶液を、ガラス繊維、アラ
ミッド繊維のような多孔質絶縁材に塗布・含浸した後、
乾燥して溶剤を除去しつつ樹脂をＢステージ化してプリ
プレグ状に仕上げる方法や、特開平４−２９６５４２号
公報に示されるように、無溶剤で高粘度の熱硬化性樹脂
を加熱溶融して、基材に含浸してプリプレグを得るいわ
ゆるホットメルト法と呼ばれる方法がある。2. Description of the Related Art Conventionally, prepregs used as insulation for electric equipment include, for example, epoxy resin, polyester resin, and the like as disclosed in JP-A-2-34639.
After applying and impregnating a solution obtained by dissolving a generally known thermosetting resin such as a silicone resin or a polyimide resin in a solvent, to a porous insulating material such as glass fiber or aramid fiber,
A method of drying and removing a solvent to form a B-stage resin and finishing it in a prepreg shape, or as shown in JP-A-4-296542, heat-melting a high-viscosity thermosetting resin without a solvent, There is a so-called hot-melt method in which a prepreg is obtained by impregnating a base material.
【０００３】[0003]
【発明が解決しようとする課題】上記溶剤を使用してプ
リプレグを製造する方法では、多量の溶剤を取り扱うた
め人体への影響や公害問題のみならず、乾燥設備、エネ
ルギー費等がかかる他、品質的には溶剤を完全に除去す
ることはきわめて困難であるため、硬化物の特性が悪い
ばかりでなく、加熱工程を経てＢステージ化した樹脂は
低温でも徐々に反応が進行するため、長期保管しにくい
という欠点がある。In the method of producing a prepreg using the above-mentioned solvent, a large amount of the solvent is used, so that not only the effect on the human body and the problem of pollution are required, but also drying equipment, energy costs, etc. are required. Since it is extremely difficult to completely remove the solvent, not only the properties of the cured product are poor, but also the resin that has been B-staged through the heating step gradually reacts even at low temperatures, so it must be stored for a long time. There is a disadvantage that it is difficult.
【０００４】また、上記ホットメルト法では、溶剤を使
用しないため人体への影響、公害問題、設備費用等の問
題は改善されているものの、高粘度もしくは半固形の樹
脂を加熱溶融して硬化剤を配合したコンパウンドを作
り、基材に含浸する際は再びコンパンドを加熱溶融する
ため、加熱溶融時のプロセス（温度、時間）管理が厳し
いこと、及び一旦加熱した樹脂は保管中に徐々に反応が
進み、長期保管できにくいという欠点のほか、高粘度の
樹脂を含浸するため基材の細部に樹脂が含浸されず品質
上の問題が生じていた。[0004] In the hot melt method, although no solvent is used, the effects on the human body, pollution problems and equipment costs are improved, but a high viscosity or semi-solid resin is heated and melted to form a curing agent. When impregnating the base material, the compound is heated and melted again, so that the process (temperature and time) during heat melting is strictly controlled, and the resin once heated gradually reacts during storage. In addition to the disadvantage that it is difficult to store for a long period of time, since the resin is impregnated with a high-viscosity resin, the details of the base material are not impregnated with the resin, causing a quality problem.
【０００５】この発明は従来の問題点を解消するために
なされたもので、無溶剤の樹脂を使用し、基材への含浸
は常温で行い、かつ加熱工程を省略して短時間の保管の
みでタックフリーに仕上げ、常温での保管寿命の長いプ
リプレグを提供することを目的とする。The present invention has been made to solve the conventional problems, and uses a solvent-free resin, impregnates a substrate at room temperature, omits a heating step, and stores only for a short time. The purpose of the present invention is to provide a prepreg having a tack-free finish and a long storage life at room temperature.
【０００６】この発明は上記のような問題を解消するた
めになされたものであり、常温で各種の基材類に含浸で
きるような粘度を有し、基材への含浸後は短時間で反応
が進みプリプレグと成り、しかもプリプレグ状での保管
寿命がきわめて長いという従来技術では到底達し得ない
特徴を有するエポキシ樹脂組成物を開発したものであ
る。The present invention has been made in order to solve the above-mentioned problems, and has a viscosity such that various substrates can be impregnated at room temperature. This has led to the development of an epoxy resin composition having a characteristic that prepregs have a very long storage life in the prepreg shape, which is hardly attainable by conventional techniques.
【０００７】[0007]
【課題を解決するための手段】請求項１に係るマイカテ
ープの製造方法は、エポキシ樹脂に有機金属塩を配合し
て成る組成物を塗布・含浸し、一方、裏打ち材に、常温
で液状のエポキシ樹脂に、常温で硬化タイプでかつ常温
で液状のアミン系硬化剤である第１の硬化剤と、マイク
ロカプセルに封入された高反応性の硬化剤又はこのマイ
クロカプセル化された硬化剤と常温で固形の潜在性硬化
剤を微粉砕したもの又は有機金属塩硬化剤の少なくとも
何れか一つからなる第２の硬化剤とを配合した組成物
を、常温で塗工処理した後、集成マイカ箔と裏打ち材と
を貼り合わせて成るものである。According to a first aspect of the present invention, there is provided a method for producing a mica tape, which comprises applying and impregnating a composition comprising an epoxy resin and an organometallic salt, and applying a liquid material at room temperature to a backing material. A first curing agent which is an amine-based curing agent which is a curing type at room temperature and which is liquid at room temperature, and a highly reactive curing agent encapsulated in microcapsules or the microencapsulated curing agent in an epoxy resin at room temperature A composition prepared by finely pulverizing a solid latent curing agent or a composition comprising at least one of an organic metal salt curing agent and a second curing agent is applied at room temperature, and then the mica foil is assembled. And a backing material.
【０００８】この発明におけるエポキシ樹脂組成物は、
ビスフェノールＡ系、ビスフェノールＦ系、ノボラック
系、シクロ系のエポキシ樹脂の単体及び各々を組み合わ
せて使用でき、いずれもエポキシ当量が１６０〜３００
で常温で液状のものが用いられる。[0008] The epoxy resin composition of the present invention comprises:
Bisphenol A-based, bisphenol F-based, novolak-based, and cyclo-based epoxy resins can be used alone or in combination, each having an epoxy equivalent of 160 to 300.
And a liquid at room temperature is used.
【０００９】また、第１の硬化剤となるアミン系硬化剤
としては、変性脂肪族アミン、変性脂環族アミン、変性
芳香族アミンが用いられ、いずれも常温で液状のものが
使用できる。これらの硬化剤はエポキシ樹脂の理論量に
対し１０〜４０％を配合し、エポキシ樹脂とアミン類が
常温で比較的速やかに反応することによって安定したＢ
ステージ状態が形成できる。これはエポキシ樹脂と少量
のアミン系硬化剤との反応が、アミド基（−ＮＨ2）の
中の１つの活性水素原子と優先的に反応し、次いで他の
水素原子も徐々に反応が進み、理論量よりも少ないにも
かかわらずやがてゲル化に至るタイプと、アミド基（−
ＮＨ2）中の活性水素原子が優先的に反応した後、残る
水素原子はもはや常温では反応せず極めて安定な状態に
なるという２つの現象のある事を見いだしたものであ
る。後者のような性状を示す物質は、分子中に立体障害
を起こし易い構造のものが有効であり、直鎖状の分子よ
りも分岐鎖のある分子が、ベンゼン環・シクロ環よりも
これらの芳香環にメチル基のような低分子のアルキル基
を付加した分子の方が顕著な作用を示す。かくしてこの
ような硬化剤を選択使用することによりタックフリーな
樹脂が容易にできるものである。なお、これらの硬化剤
の中でも硬化組成物の電気的、機械的、熱的性質に優れ
たものを得る際は、アミン系硬化剤中変性脂環族アミン
が好適であり、例えば、ジアミノジフェニールメタンの
水添化物やシクロ環中にメチル基を置換したタイプが特
に好適に用いられる。As the amine-based curing agent serving as the first curing agent, modified aliphatic amines, modified alicyclic amines, and modified aromatic amines are used, and any of them can be used at room temperature. These hardeners are blended in an amount of 10 to 40% based on the theoretical amount of the epoxy resin, and the epoxy resin and amines react relatively quickly at room temperature to form a stable B.
A stage state can be formed. This reaction between the epoxy resin and a minor amount of amine curing agent, reacts preferentially with one of the active hydrogen atoms in the amide groups (-NH 2), then the other hydrogen atom gradually reaction proceeds, In spite of the fact that it is less than the stoichiometric amount, the type that eventually leads to gelation and the amide group (-
It has been found that after active hydrogen atoms in NH 2 ) react preferentially, the remaining hydrogen atoms no longer react at room temperature and become extremely stable. It is effective for the substance having the latter property to have a structure that easily causes steric hindrance in the molecule, and a molecule having a branched chain is more likely to have a fragrance than a benzene ring or a cyclo ring than a linear molecule. Molecules in which a low molecular weight alkyl group such as a methyl group is added to the ring have a more remarkable effect. Thus, by selectively using such a curing agent, a tack-free resin can be easily obtained. Among these curing agents, when obtaining a cured composition having excellent electrical, mechanical, and thermal properties, an amine-based curing agent-modified alicyclic amine is preferable, for example, diaminodiphenyl A hydrogenated product of methane or a type obtained by substituting a methyl group in a cyclo ring is particularly preferably used.
【００１０】用いる硬化剤量としては、エポキシ樹脂の
理論量に対する割合が１０％以下の場合は、樹脂組成物
の粘度上昇が少なく所望のタックフリーな樹脂が得られ
難い。また、４０％以上の場合は、樹脂組成物の反応が
進みゲル化に至る場合があり好ましくない。用いるベー
ス樹脂の性状にもよるが、通常は２０〜３３％の範囲で
プリプレグの固さ、しなやかさを勘案しながら配合量を
決める。When the amount of the curing agent used is 10% or less based on the theoretical amount of the epoxy resin, the increase in viscosity of the resin composition is so small that it is difficult to obtain a desired tack-free resin. On the other hand, when the content is 40% or more, the reaction of the resin composition may proceed to cause gelation, which is not preferable. Although it depends on the properties of the base resin used, the amount is usually determined within the range of 20 to 33% in consideration of the hardness and flexibility of the prepreg.
【００１１】かかる樹脂系の第２の硬化剤としては、次
に例示するような触媒系によるイオン反応で進行するも
のが多い。すなわち通常知られているＢＦ3−モノエチ
ルアミン及びその誘導体、ジシアンジアミド、ヒドラジ
ド類、及びアミンアダクト類と呼ばれる高分子量、かつ
アミド基を含有するいずれも常温で固体の化合物が用い
られる。実使用時にはこれらの硬化剤を樹脂中に分散さ
せるために微粉末にしたものが好適に用いられる。Many of the resin-based second curing agents proceed by an ionic reaction using a catalyst system as exemplified below. That is, generally known BF 3 -monoethylamine and its derivatives, dicyandiamide, hydrazides, and amine adducts, all of which have a high molecular weight and which contain an amide group, are solid at room temperature. At the time of actual use, a fine powder is preferably used in order to disperse these curing agents in the resin.
【００１２】また、イミダゾール類のような高反応性の
硬化剤をポリビニールホルマール、イソシアネート類、
ポリカーボネート等に包み込みマイクロカプセル化し
て、２〜５μmmに仕上げた硬化剤も使用できる。これは
カプセルの外皮を加熱溶融させるまで反応を開始しない
ためプリプレグ適用後は、安定した樹脂系と成るという
特徴があり、極めて好適に使用できる。Further, a highly reactive curing agent such as imidazoles may be used in the form of polyvinyl formal, isocyanates,
It is also possible to use a curing agent which is wrapped in polycarbonate or the like and microencapsulated, and finished to 2 to 5 μm. This is characterized in that since the reaction does not start until the outer shell of the capsule is heated and melted, it becomes a stable resin system after application of the prepreg, and can be used very suitably.
【００１３】更に、常温でエポキシ樹脂とほとんど反応
しないが高温では硬化剤・触媒作用を持つオクチル酸亜
鉛、ナフテン酸マンガン、鉄アセチルアセトナートのよ
うな通常知られている有機金属塩が良好に用いられる。Further, commonly known organic metal salts such as zinc octylate, manganese naphthenate, and iron acetylacetonate, which hardly react with the epoxy resin at room temperature but have a hardening agent / catalytic action at high temperature, are preferably used. Can be
【００１４】これらの硬化剤は、それぞれ単独で、又は
要求する硬化物の特性により組み合わせて使用できる事
は言うまでもない。It goes without saying that these curing agents can be used alone or in combination depending on the required properties of the cured product.
【００１５】通常、エポキシ樹脂に対して２種類の硬化
剤を配合した場合は、活性度の高い硬化剤が先に反応す
るため、活性度の低い（硬化の遅い）硬化剤は反応系中
より取り残され、結果として未反応の硬化剤が残るの
で、電気的、機械的、熱的諸特性の悪い硬化物となる。
この発明によるエポキシ樹脂組成物は、第１及び第２の
硬化剤の相乗効果、特に第２の反応が起こる際のイオン
反応と分子中に残る水素基の影響によりそれぞれの硬化
剤を単独で配合してなる系よりも、硬化物は諸特性の優
れたものが得られることを確認し、この発明を完成し
た。Usually, when two types of curing agents are mixed with an epoxy resin, a curing agent having a high activity reacts first, so that a curing agent having a low activity (slow curing) is used in the reaction system. Since the unreacted curing agent remains as a result, the cured product has poor electrical, mechanical and thermal properties.
The epoxy resin composition according to the present invention contains each of the curing agents alone due to the synergistic effect of the first and second curing agents, particularly the ionic reaction when the second reaction occurs and the effect of the hydrogen groups remaining in the molecule. It has been confirmed that a cured product having excellent properties can be obtained as compared with the system formed by the method described above, and the present invention has been completed.
【００１６】上記発明のエポキシ樹脂組成物において
は、第１の硬化剤の配合量の変化で所望の粘度のプリプ
レグを容易に作成することができるので、次のような特
徴を持つドライタイプの集成マイカテープの製造に適用
できる。In the epoxy resin composition of the present invention, since a prepreg having a desired viscosity can be easily prepared by changing the amount of the first curing agent, a dry-type assembly having the following characteristics is provided. Applicable to manufacture of mica tape.
【００１７】集成マイカ箔は、通常知られているエポキ
シ樹脂に有機金属塩を配合して成るエポキシ樹脂組成物
を溶剤タイプで塗布・含浸した後乾燥して仕上げるが、
裏打ち材側には上記発明のエポキシ樹脂組成物中、含浸
樹脂との反応促進効果の高い、例えば第２の硬化剤とし
てイミダゾール類をマイクロカプセル化したものを用い
無溶剤タイプで含浸処理し、これを集成マイカと貼り合
わせることによって得られる。このマイカテープを高電
圧回転機用絶縁コイルに巻回適用し、含浸樹脂として多
用されているエポキシ樹脂に酸無水物系硬化剤及びこれ
にスチレンのような反応性希釈剤を含有して成る含浸樹
脂を真空加圧・含浸後、加熱硬化して絶縁コイルを得る
ものである。即ち、前記含浸樹脂と反応促進効果の高い
イミダゾール類はエポキシ樹脂と容易に反応するため、
通常はテープ寿命の要求されるマイカテープには使用さ
れず、やむなく使用する場合は、ベース樹脂としてポリ
エステル樹脂のようなイミダゾール類とはほとんど反応
しない樹脂を選択している。しかしながら前記エポキシ
含浸樹脂と比べ含浸・硬化後に耐熱性、接着性等の特性
に劣るポリエステル樹脂が混入することは絶縁コイルの
品質を低下させることになるので実際は実用されていな
い。イミダゾール類の外皮を成すマイクロカプセルは通
常の溶剤に容易に溶けるため、含浸樹脂中にスチレンを
含有する樹脂系は樹脂が含浸されると常温でも反応が開
始され始めるので反応促進効果は更に加速され、絶縁処
理の簡略化効果は多大となる。The laminated mica foil is finished by coating and impregnating an epoxy resin composition obtained by blending an organic metal salt with a generally known epoxy resin in a solvent type, followed by drying.
On the backing material side, the epoxy resin composition of the present invention has a high reaction promoting effect with the impregnating resin, for example, a non-solvent type impregnating treatment using a microcapsulated imidazole as the second curing agent, Is obtained by laminating with mica. This mica tape is wound around an insulating coil for a high-voltage rotating machine, and impregnated by containing an acid anhydride-based curing agent and a reactive diluent such as styrene into an epoxy resin, which is frequently used as an impregnating resin. After the resin is vacuum-pressed and impregnated, it is cured by heating to obtain an insulating coil. That is, because the impregnated resin and imidazoles having a high reaction promoting effect easily react with the epoxy resin,
Normally, mica tapes that require a long tape life are not used, and when used unavoidably, resins that hardly react with imidazoles, such as polyester resins, are selected as base resins. However, the incorporation of a polyester resin having inferior properties such as heat resistance and adhesiveness after impregnation and curing as compared with the epoxy impregnated resin impairs the quality of the insulating coil, and is not practically used. Since the microcapsules forming the outer skin of imidazoles are easily dissolved in ordinary solvents, the reaction-promoting effect of the resin system containing styrene in the impregnated resin is further accelerated when the resin is impregnated, even at room temperature, so that the reaction promoting effect is further accelerated. In addition, the effect of simplifying the insulation process is great.
【００１８】なお、この発明ではイミダゾール類以外で
も、使用する含浸樹脂に合わせて硬化促進効果を勘案す
ることにより適宜第２の硬化剤が選択使用できる。In the present invention, other than the imidazoles, the second curing agent can be appropriately selected and used in consideration of the effect of accelerating the curing in accordance with the impregnating resin to be used.
【００１９】[0019]
【実施の形態】実施例１．ビスフェノールＡ型エポキシ
樹脂としてエピコート８２８（エポキシ当量１９０ｇ/
ｅｑ、油化シェル社）１００部、第１の硬化剤としてエ
ピキュアー１１３（水添化ジアミノジフェニールメタン
誘導体、粘度１２５ｃｐｓ／２５℃、油化シェル社）１
０部、第２の硬化剤としてノバキュアーＨＸ３７２２
（イミダゾールのマイクロカプセルタイプ、ペースト
状、旭化成社）２０部を常温で混合した。これを厚さ
０.１８ｍｍのガラスクロス（有沢製作所社）にレジン
含有量５０％となるように常温で塗布し、３０℃で保管
して２４時間後にタックフリーなプリプレグを得た。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiment 1 FIG. Epicoat 828 (epoxy equivalent 190 g /
eq, Yuka Shell Co.) 100 parts, Epicur 113 (hydrogenated diaminodiphenyl methane derivative, viscosity 125 cps / 25 ° C., Yuka Shell Co.) as a first curing agent
0 parts, Novacur HX3722 as a second curing agent
20 parts (microcapsule type of imidazole, paste, Asahi Kasei Corporation) were mixed at room temperature. This was applied to a glass cloth (Arisawa Seisakusho) having a thickness of 0.18 mm at room temperature so as to have a resin content of 50%, and stored at 30 ° C. to obtain a tack-free prepreg after 24 hours.
【００２０】実施例２．ビスフェノールＦ型エポキシ樹
脂としてエピコート８０７（エポキシ当量１６７ｇ／ｅ
ｑ、油化シェル社）１００部、第１の硬化剤としてエピ
キュアー１１３（前出）１１部、第２の硬化剤としてノ
バキュアーＨＸ３７２２（前出）２０部を常温で混合し
た。これを厚さ０.１８ｍｍのガラスクロス（前出）に
レジン含有量５０％となるように常温で塗布し、３０℃
で保管して２４時間後にタックフリーなプリプレグを得
た。Embodiment 2 FIG. Epicoat 807 (epoxy equivalent 167 g / e) as a bisphenol F type epoxy resin
q, Yuka Shell Co., Ltd.), 100 parts of Epicur 113 (described above) as a first curing agent, and 20 parts of Novacur HX3722 (described above) as a second curing agent were mixed at room temperature. This was applied to a glass cloth (described above) having a thickness of 0.18 mm at room temperature so as to have a resin content of 50%.
After 24 hours, a tack-free prepreg was obtained.
【００２１】実施例３．エピコート８２８（前出）５０
部、ノボラック型エポキシ樹脂としてエピコート１５２
（エポキシ当量１７５ｇ／ｅｑ、油化シェル社）５０
部、第１の硬化剤としてエピキュアー１１３（前出）１
１部、第２の硬化剤としてノバキュアーＨＸ３７２２
（前出）２０部を常温で混合した。これを厚さ０.１８
ｍｍのガラスクロス（前出）にレジン含有量５０％とな
るように常温で塗布し、３０℃で保管して２４時間後タ
ックフリーなプリプレグを得た。Embodiment 3 FIG. Epicoat 828 (see above) 50
Part, Epicoat 152 as novolak type epoxy resin
(Epoxy equivalent: 175 g / eq, Yuka Shell Co.) 50
Part, Epicur 113 (described above) 1 as the first curing agent
1 part, Novacur HX3722 as second curing agent
Twenty parts were mixed at room temperature. This has a thickness of 0.18
The resin was applied to a 50 mm glass cloth (described above) at room temperature so as to have a resin content of 50%, and stored at 30 ° C. to obtain a tack-free prepreg after 24 hours.
【００２２】実施例４．エピコート８２８（前出）１０
０部、第１の硬化剤としてエピキュアー３０８０（変性
脂肪族アミン、粘度８.０ｃｐｓ／２５℃、油化シェル
社）１１部、第２の硬化剤としてノバキュアーＨＸ３７
２２（前出）２０部を常温で混合した。これを厚さ０.
１８ｍｍのガラスクロス（前出）にレジン含有量５０％
となるように常温で塗布し、３０℃で保管して２４時間
後タックフリーなプリプレグを得た。Embodiment 4 FIG. Epicoat 828 (see above) 10
0 parts, Epicure 3080 (modified aliphatic amine, viscosity 8.0 cps / 25 ° C., Yuka Shell Co.) as a first curing agent, Novacur HX37 as a second curing agent
Twenty parts (22) were mixed at room temperature. Thick this to a thickness of 0.
Resin content of 50% in 18mm glass cloth (see above)
After applying for 24 hours at 30 ° C., a tack-free prepreg was obtained.
【００２３】実施例５．エピコート８２８（前出）５０
部、ノボラック型エポキシ樹脂としてエピコート１５２
（前出）５０部、第１の硬化剤としてエピキュアー１１
３（前出）１１部、第２の硬化剤としてジシアンジアミ
ドの微粉末（油化シェル社）６部及び、触媒としてノバ
キュアーＨＸ３７２２（前出）４部を常温で混合した。
これを厚さ０.１８ｍｍのガラスクロス（前出）にレジ
ン含有量５０％となるように常温で塗布し、３０℃で保
管して２４時間後タックフリーなプリプレグを得た。Embodiment 5 FIG. Epicoat 828 (see above) 50
Part, Epicoat 152 as novolak type epoxy resin
(Supra) 50 parts, Epicur 11 as the first curing agent
3 (described above), 6 parts of dicyandiamide fine powder (Yuka Shell Co., Ltd.) as a second curing agent, and 4 parts of NOVACURE HX3722 (described above) as a catalyst were mixed at room temperature.
This was applied to a glass cloth (described above) having a thickness of 0.18 mm so as to have a resin content of 50% at room temperature, and stored at 30 ° C. to obtain a tack-free prepreg after 24 hours.
【００２４】比較例１．ビスフェノールＡ型エポキシ樹
脂としてエピコート８３４（エポキシ当量２５０ｇ／ｅ
ｑ、油化シェル社）４０部、エピコート１００１（エポ
キシ当量４７５ｇ／ｅｑ、油化シェル社）６０部にメチ
ルエチルケトン６０部を加えて溶解し、硬化剤としてジ
シアンジアミド（前出）６部、触媒として３，４−ジク
ロルフェニル−１，１−ジメチルウレア（油化シェル
社）０.３部をあらかじめメチルセロソルブ３０部に溶
解しておいた溶液を混合してワニスを調合した。これを
厚さ０.１８ｍｍのガラスクロス（前出）にレジン含有
量５０％となるように常温で塗布し、次いで１００〜１
３５℃で７分間乾燥してタックフリーなプリプレグ（残
存溶剤量０.２％）を得た。Comparative Example 1 Epicoat 834 (epoxy equivalent 250 g / e) as bisphenol A type epoxy resin
q, 40 parts of Epicoat 1001 (epoxy equivalent: 475 g / eq, Yuka Shell) and 60 parts of methyl ethyl ketone were dissolved in 40 parts of Epicoat 1001 and 60 parts of dicyandiamide (described above) as a curing agent and 3 parts as a catalyst. A solution prepared by dissolving 0.3 part of 1,4-dichlorophenyl-1,1-dimethylurea (Yuika Shell Co., Ltd.) in 30 parts of methyl cellosolve in advance was mixed to prepare a varnish. This was applied at room temperature to a 0.18 mm thick glass cloth (described above) so that the resin content was 50%.
After drying at 35 ° C. for 7 minutes, a tack-free prepreg (residual solvent amount: 0.2%) was obtained.
【００２５】比較例２．エポキシ樹脂としてエピコート
８３４（前出）２５部に、エピコート１００１（前出）
７５部を加え６５℃で混合し、硬化剤としてノバキュア
ーＨＸ３７２２（前出）３０部を加え同じ温度で素早く
混練した。これを厚さ０.１８ｍｍのガラスクロス（前
出）にレジン含有量５０％となるように６５℃〜７５℃
で塗布し、タックフリーなプリプレグを得たが、高粘度
であるため基剤への塗布作業性はきわめて悪く、また仕
上がり状態も塗りムラが多くあった。Comparative Example 2 25 parts of Epicoat 834 (described above) as an epoxy resin and Epicoat 1001 (described above)
75 parts were added and mixed at 65 ° C., 30 parts of NOVACURE HX3722 (described above) as a curing agent was added, and the mixture was quickly kneaded at the same temperature. This is placed on a 0.18 mm thick glass cloth (described above) at 65 to 75 ° C. so that the resin content is 50%.
To obtain a tack-free prepreg. However, because of the high viscosity, the workability of application to the base was extremely poor, and the finished state had many coating irregularities.
【００２６】この出願の発明の効果を確認するために、
実施例及び比較例で得られたプリプレグの３０℃での保
管寿命を樹脂がゲル化するまでの時間（日数）で表し、
またプリプレグの５枚を重ねて１５０℃で５時間加熱成
形して厚さ１.０ｍｍの積層板を得た。この積層板の仕
上がり状態及び熱進入法によるガラス転位温度（Ｔｇ）
の結果を図１に示したが、この発明によるプリプレグは
従来から知られているプリプレグと比較していずれの特
性も優れていることを確認した。In order to confirm the effects of the invention of this application,
The storage life at 30 ° C. of the prepregs obtained in Examples and Comparative Examples is represented by the time (days) until the resin gels,
Also, five prepregs were stacked and heated and formed at 150 ° C. for 5 hours to obtain a laminate having a thickness of 1.0 mm. Finished state of this laminate and glass transition temperature (Tg) by heat penetration method
As shown in FIG. 1, it was confirmed that the prepreg according to the present invention was superior to any conventionally known prepreg in all properties.
【００２７】実施例６．本実施例はマイカテープの製造
方法に係るもので、エポキシ樹脂としてエピコート８３
４（前出）４０部、エピコート１００１（前出）６０部
に硬化剤としてオクチル酸亜鉛１０部、メチルエチルケ
トン１６０部を加え溶解してワニスを調合した。これを
厚さ０.１０ｍｍの集成マイカ箔（無焼成タイプＤＲ−
２、岡部マイカ工業所）にレジン含有量５％となるよう
に塗布した後、８０℃〜１２０℃で７分間乾燥した。マ
イカ箔の裏打ち材として厚さ０.０３ｍｍのガラスクロ
ス（有沢製作所）にエピコート８２８（前出）１００
部、第１の硬化剤としてエピキュアー１１３（前出）１
０部、第２の硬化剤としてオクチル酸亜鉛１０部及びノ
バキュアーＨＸ３７２２（前出）１０部を常温で混練し
た組成物を塗布してレジン含有量１５％となるように仕
上げ、これを前記のマイカ箔に処理したプリプレグと重
ね、５０℃に調整したヒートロールを通過させて貼り合
わせることにより厚さ０.１３５ｍｍ、レジン含有量７.
５％のマイカテープを製作した。Embodiment 6 FIG. This example relates to a method for manufacturing a mica tape, and uses Epicoat 83 as an epoxy resin.
4 parts (described above) and 60 parts of Epicoat 1001 (described above) were added with 10 parts of zinc octylate and 160 parts of methyl ethyl ketone as curing agents and dissolved to prepare a varnish. This is assembled with 0.10 mm thick mica foil (non-fired type DR-
2, Okabe Mica Industrial Co., Ltd.), and dried at 80 ° C. to 120 ° C. for 7 minutes. Epicoat 828 (supra) 100 on 0.03 mm thick glass cloth (Arisawa Seisakusho) as a backing material of mica foil
Part, Epicur 113 (described above) 1 as the first curing agent
0 parts, 10 parts of zinc octylate as a second curing agent and 10 parts of NOVACURE HX3722 (described above) were kneaded at room temperature, and the composition was applied to a resin content of 15%. It is put on a prepreg that has been processed into a foil, passed through a heat roll adjusted to 50 ° C., and bonded to each other to have a thickness of 0.135 mm and a resin content of 7.
A 5% mica tape was produced.
【００２８】このマイカテープを厚さ２.０ｍｍ×７.０
ｍｍの平角２重ガラス巻線（三菱電線）を２列２０段に
組み合わせた長さ１.０Ｍのコイル導体上に１０回巻
き、マイカテープの保護として厚さ０.１３ｍｍのガラ
ステープを１回巻いた後、ビスフェノールＡ型エポキシ
樹脂／酸無水物系硬化剤／スチレンモノマーを主成分と
するスチレン変性エポキシ含浸樹脂（ＤＲ３１１、菱電
化成）中で真空加圧含浸処理した後、１３５℃で２４時
間加熱して絶縁コイルを得た。この絶縁コイルのＴａｎ
δ（２ＫＶ値）及びΔＴａｎδ（１５ＫＶ−２ＫＶ値）
はそれぞれ０.５８％、０.１０％と非常に良好であっ
た。This mica tape is 2.0 mm thick × 7.0 mm thick.
mm flat rectangular double glass winding (Mitsubishi Electric Wire) is wound 10 times on a 1.0M long coil conductor in two rows and 20 steps, and 0.13mm thick glass tape is used once to protect the mica tape. After being wound, it is impregnated with a vacuum pressure in a styrene-modified epoxy impregnated resin (DR311, Ryoden Kasei) containing a bisphenol A type epoxy resin / anhydride-based curing agent / styrene monomer as a main component. After heating for an hour, an insulating coil was obtained. Tan of this insulated coil
δ (2KV value) and ΔTan δ (15KV-2KV value)
Was very good, 0.58% and 0.10%, respectively.
【００２９】比較例３．エポキシ樹脂としてエピコート
８３４（エポキシ当量２５０ｇ／ｅｑ、油化シェル社）
４０部、エピコート１００１（エポキシ当量４７５ｇ／
ｅｑ、油化シェル社）６０部に硬化剤としてオクチル酸
亜鉛１０部、メチルエチルケトン１６０部を加え溶解し
てワニスを調合した。これを厚さ０.１０ｍｍの集成マ
イカ箔（無焼成タイプＤＲ−２、岡部マイカ工業所）に
レジン含有量５％となるように塗布した後、８０℃〜１
２０℃で７分間乾燥した。マイカ箔の裏打ち材として厚
さ０.０３ｍｍのガラスクロス（前出）に前記のエポキ
シ組成物を塗布した後、８０℃〜１２０℃で７分間乾燥
してレジン含有量１５％となるように仕上げ、これを前
記のマイカ箔に処理したプリプレグと重ね、５０℃に調
整したヒートロールを通過させて貼り合わせることによ
り厚さ０.１３５ｍｍ、レジン含有量７.５％のマイカテ
ープを製作した。Comparative Example 3 Epicoat 834 (epoxy equivalent 250g / eq, Yuka Shell Co., Ltd.) as epoxy resin
40 parts, Epicoat 1001 (epoxy equivalent 475 g /
eq, Yuka Shell Co., Ltd.), 60 parts of zinc octylate and 160 parts of methyl ethyl ketone were added and dissolved as a curing agent to prepare a varnish. This was applied to a laminated mica foil having a thickness of 0.10 mm (non-fired type DR-2, Okabe Mica Kogyosho) so as to have a resin content of 5%.
Dry at 20 ° C. for 7 minutes. After applying the above epoxy composition to a 0.03 mm-thick glass cloth (described above) as a backing material of mica foil, drying at 80 ° C. to 120 ° C. for 7 minutes to finish to a resin content of 15%. This was overlapped with the prepreg treated on the above mica foil, passed through a heat roll adjusted to 50 ° C., and bonded to produce a mica tape having a thickness of 0.135 mm and a resin content of 7.5%.
【００３０】このマイカテープを厚さ２.０ｍｍ×７.０
ｍｍの平角２重ガラス巻線（前出）を２列２０段に組み
合わせた長さ１.０Ｍのコイル導体上に１０回巻き、マ
イカテープの保護として厚さ０.１３ｍｍのガラステー
プを１回巻いた後、スチレン変性エポキシ含浸樹脂（前
出）中で真空加圧含浸処理した後、１３５℃で２４時間
加熱して絶縁コイルを得た。この絶縁コイルのＴａｎδ
（２ＫＶ値）及びΔＴａｎδ（１５ＫＶ−２ＫＶ値）は
それぞれ０.７８％、１．５０％であった。This mica tape was 2.0 mm thick × 7.0 mm thick.
10 mm on a coil conductor with a length of 1.0 M, which is a combination of 20 mm flat rectangular double glass windings (shown above) in two rows and 20 steps, and using 0.13 mm thick glass tape once to protect the mica tape After being wound, it was subjected to vacuum pressure impregnation in a styrene-modified epoxy impregnated resin (described above), and then heated at 135 ° C. for 24 hours to obtain an insulating coil. Tanδ of this insulating coil
(2KV value) and ΔTanδ (15KV-2KV value) were 0.78% and 1.50%, respectively.
【００３１】[0031]
【発明の効果】この発明のマイカテープの製造方法によ
って作成された絶縁コイルは、マイカテープの裏打ち材
側に含浸樹脂との反応促進効果の大きいプリプレグ組成
物を含有するため、真空加圧含浸後の加熱時には含浸樹
脂の粘度低下と同時に硬化反応が進むので絶縁層中の樹
脂漏れを起こさない。その結果、絶縁層中にほとんど気
泡の無い良好なものが得られる。The insulated coil produced by the method for producing a mica tape of the present invention contains a prepreg composition having a large effect of accelerating the reaction with the impregnating resin on the backing material side of the mica tape. During the heating, the curing reaction proceeds simultaneously with the decrease in the viscosity of the impregnated resin, so that the resin does not leak in the insulating layer. As a result, a good product having almost no bubbles in the insulating layer can be obtained.
【図１】この発明の実施例と比較例との保管寿命、仕上
り状態及びガラス転移温度を示す図である。FIG. 1 is a diagram showing the shelf life, finished state, and glass transition temperature of an example of the present invention and a comparative example.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） // Ｂ２９Ｋ 463:00 Ｃ０８Ｌ 63:00 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) // B29K 463: 00 C08L 63:00
Claims (1)
る組成物を塗布・含浸し、一方、裏打ち材に、常温で液
状のエポキシ樹脂に、常温で硬化タイプでかつ常温で液
状のアミン系硬化剤である第１の硬化剤と、マイクロカ
プセルに封入された高反応性の硬化剤又はこのマイクロ
カプセル化された硬化剤と常温で固形の潜在性硬化剤を
微粉砕したもの又は有機金属塩硬化剤の少なくとも何れ
か一つからなる第２の硬化剤とを配合した組成物を、常
温で塗工処理した後、上記集成マイカ箔と上記裏打ち材
とを貼り合わせて成るマイカテープの製造方法。1. An epoxy resin mixed with an organic metal salt is applied and impregnated. On the other hand, an epoxy resin which is liquid at room temperature, an epoxy resin which is liquid at room temperature, and an amine resin which is liquid at room temperature A first curing agent which is a curing agent, a highly reactive curing agent encapsulated in microcapsules, or a finely pulverized one of the microencapsulated curing agent and a latent curing agent which is solid at room temperature, or an organic metal salt A method for producing a mica tape comprising applying a composition containing at least one of a curing agent and a second curing agent at room temperature, and then laminating the laminated mica foil and the backing material. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14283699A JP2000026630A (en) | 1999-05-24 | 1999-05-24 | Production of mica tape |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14283699A JP2000026630A (en) | 1999-05-24 | 1999-05-24 | Production of mica tape |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5321262A Division JP3046905B2 (en) | 1993-11-26 | 1993-11-26 | Pre-preg for electrical insulation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000026630A true JP2000026630A (en) | 2000-01-25 |
Family
ID=15324754
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14283699A Pending JP2000026630A (en) | 1999-05-24 | 1999-05-24 | Production of mica tape |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2000026630A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001063624A1 (en) * | 2000-02-24 | 2001-08-30 | Siemens Westinghouse Power Corporation | Enhanced dielectric strength mica tapes |
| CN105047256A (en) * | 2015-06-30 | 2015-11-11 | 株洲时代新材料科技股份有限公司 | Mica tape containing microcapsule curing accelerator and preparation method thereof |
| CN105788704A (en) * | 2015-12-31 | 2016-07-20 | 苏州巨峰电气绝缘***股份有限公司 | Modified mica tape |
-
1999
- 1999-05-24 JP JP14283699A patent/JP2000026630A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001063624A1 (en) * | 2000-02-24 | 2001-08-30 | Siemens Westinghouse Power Corporation | Enhanced dielectric strength mica tapes |
| CN105047256A (en) * | 2015-06-30 | 2015-11-11 | 株洲时代新材料科技股份有限公司 | Mica tape containing microcapsule curing accelerator and preparation method thereof |
| CN105788704A (en) * | 2015-12-31 | 2016-07-20 | 苏州巨峰电气绝缘***股份有限公司 | Modified mica tape |
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